CN116553614A - Preparation method and device of tantalum pentachloride - Google Patents
Preparation method and device of tantalum pentachloride Download PDFInfo
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- CN116553614A CN116553614A CN202310451548.7A CN202310451548A CN116553614A CN 116553614 A CN116553614 A CN 116553614A CN 202310451548 A CN202310451548 A CN 202310451548A CN 116553614 A CN116553614 A CN 116553614A
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- tantalum pentachloride
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- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 36
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 23
- 239000010959 steel Substances 0.000 claims description 23
- 238000005070 sampling Methods 0.000 claims description 19
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 description 15
- 238000001514 detection method Methods 0.000 description 12
- 238000011049 filling Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 229910000792 Monel Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000011172 small scale experimental method Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/02—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of tantalum pentachloride, which comprises the following steps of S1, loading tantalum into a reaction kettle, replacing gas in the reaction kettle with inert gas, and vacuumizing; s2, heating the reaction kettle, introducing chlorine or hydrogen chloride into the reaction kettle, and reacting for 1.0-5.0 hours; s3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, firstly cooling the tower kettle, controlling the temperature to be between-90 and 0 ℃, keeping the temperature for 0.5 to 3.0 hours, then heating the tower kettle at the temperature of between 200 and 650 ℃, controlling the pressure of the rectifying tower to be between 0.01 and 0.30MPa, and keeping the temperature for 0.5 to 2.0 hours; and S4, heating the tower top, and discharging after the tantalum pentachloride index is qualified. The invention also provides a preparation device of tantalum pentachloride, and compared with the existing product, the tantalum pentachloride prepared by the method and the equipment has higher purity.
Description
Technical Field
The invention belongs to the field of rare metal material preparation, and particularly relates to a preparation method and device of tantalum pentachloride.
Background
Tantalum pentachloride is an inorganic compound with a chemical formula of TaCl 5 Is white crystalline powder, is dissolved in absolute alcohol, chloroform, carbon tetrachloride, carbon disulfide, thiophenol and potassium hydroxide, and is mainly used as chlorinating agent of organic compounds, chemical intermediate and used for preparing tantalum and the like. Tantalum pentachloride is playing an important role as a rare metal material in the field of material chemistry.
Physical vapor deposition (PVD for short) is a main process for depositing metal interconnection lines of integrated circuit chips, and specifically refers to a method of vaporizing a certain substance surface into gaseous atoms, molecules or partially ionizing the gaseous atoms into ions under vacuum conditions, and depositing a thin film material with a certain special function on the substrate material surface through a low-pressure gas process, which can be divided into two methods of sputtering coating and vacuum evaporation coating according to operation techniques.
Sputtering targets are key consumables in the process. The semiconductor chip unit device is composed of a substrate, an insulating layer, a dielectric layer, a conductor layer, a protective layer and the like, wherein the dielectric layer, the conductor layer and even the protective layer are all subjected to a sputtering coating process. Targets for coating in the integrated circuit field mainly comprise tantalum targets, aluminum targets, tungsten targets and the like, and particularly 12-inch tantalum targets are almost totally dependent on import and are mainly monopolized by target manufacturing in japan and usa, accounting for about 90% of the global target market for semiconductor chips.
Tantalum pentachloride is used as tantalum silicide or tantalum film in electronic industry by chemical vapor deposition to manufacture low-resistance and high-melting-point circuit interconnection lines and grids, and can form insulating films with extremely strong adhesive force and thickness of 0.1 mu m on the surfaces of electronic components, semiconductor devices, titanium and metal nitride electrodes and tungsten, and has higher dielectric rate. Furthermore, more importantly, the high-purity tantalum pentachloride is a key raw material for preparing the high-purity tantalum target material by chemical vapor deposition (CVD for short), the service performance of the high-purity tantalum pentachloride is higher than that of tantalum pentafluoride, and tantalum pentafluoride is gradually replaced in the future.
Chinese patent 201611084954.0 proposes a method and a device for preparing high-purity low-metal impurity tantalum pentachloride by a one-step method, and the method is simple and difficult to realize large-scale continuous production, and a chlorine gas source in the process only adopts chlorine gas, so that the limitation of raw materials is increased, and the production cost is increased by hydrotreating in the process and simultaneously, the safety risk is also increased. The most critical is that the purity of tantalum pentachloride prepared by the process method is 99.95 percent at most, and the use requirement of the integrated circuit on high-purity precursor materials still cannot be met. According to the preparation method and the device for tantalum pentachloride, raw materials for preparing tantalum pentachloride are added, so that the single property of the raw materials is effectively avoided; the specific rectification equipment and the rectification method are added in the technical process, so that the purity of tantalum pentachloride can be improved to 99.999% or more while the large-scale continuous production is realized, the impurity content of tantalum pentachloride is better reduced, and the product quality and the service life of a tantalum target material taking tantalum pentachloride as a raw material are effectively improved.
To obtain high purity tantalum pentachloride is required to overcome the great technical challenges, and in view of this, research on the preparation method of tantalum pentachloride is required to overcome the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method and a device of tantalum pentachloride, and compared with the existing product, the tantalum pentachloride prepared by the method and the device has higher purity, so that the internal impurity elements in the tantalum pentachloride are prevented from being transferred to a terminal product, the stability of the terminal product is effectively improved, and the product quality of a high-purity tantalum target material taking the tantalum pentachloride as a precursor is further improved.
The technical scheme adopted by the invention is as follows:
the invention provides a preparation method of tantalum pentachloride, which comprises the following steps,
s1, loading tantalum with purity of more than 99% into a reaction kettle, controlling the loading amount to be 5% -40% of the volume of the reaction kettle, replacing gas in the reaction kettle with inert gas or nitrogen, vacuumizing, and repeating the operation for 5-20 times;
s2, heating the reaction kettle at the temperature of 300-850 ℃, introducing chlorine or hydrogen chloride into the reaction kettle, and reacting for 1.0-5.0 hours;
s3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, wherein the rectifying tower comprises a tower kettle and a tower top which is arranged above the tower kettle and is communicated with the tower kettle, firstly cooling the tower kettle, controlling the temperature to be between-90 and 0 ℃, keeping the temperature for 0.5 to 3.0 hours, then heating the tower kettle at 200 to 650 ℃, controlling the pressure of the rectifying tower to be between 0.01 and 0.30MPa, and keeping the temperature for 0.5 to 2.0 hours;
s4, heating the tower top at 100-200 ℃, maintaining the temperature for 0.5-4.0 hours, repeatedly sampling and detecting for 2-10 times, and discharging after the tantalum pentachloride index is qualified.
Further, in the step S1, the inert gas is argon or helium, and the purity is 99.0% -99.999%.
Further, in the step S1, inert gas is filled into the reaction kettle until the pressure is 0.01-0.15 MPa, and then the reaction kettle is vacuumized to-0.1 MPa.
Further, in the step S2, the purity of the introduced chlorine or hydrogen chloride is 99.0-99.9999%, the heating temperature of the reaction kettle is 350-800 ℃, the heating rate is 30-120 ℃/h, and the air inflow of the chlorine or hydrogen chloride is 2.0-8.0 kg/h.
Further, in step S4, the heating temperature at the top of the column is 110 to 190 ℃.
The invention also provides a preparation device of tantalum pentachloride, which comprises a reaction kettle and a rectifying tower, wherein the reaction kettle is connected with a chlorinated gas steel cylinder and an inert gas steel cylinder, and a discharge hole of the reaction kettle is connected with a feed hole of the rectifying tower; the rectifying tower comprises a tower kettle and a tower top which is arranged above the tower kettle and communicated with the tower kettle, and a cooling device and a heater are arranged on the tower kettle.
Further, the reaction kettle is a reaction kettle with a heating function or is connected with a heating device.
Further, the cooling device is a cooling jacket arranged on the periphery of the tower kettle, and the heater is an armored heater arranged at the bottom of the tower kettle.
Further, a reaction kettle feed inlet is arranged on the reaction kettle; the tower top is provided with a tower top sampling port and a tower top discharge port; the tower bottom and the tower top are connected through a rectification conveying pipe.
The beneficial effects of the invention are as follows:
1. the invention provides a preparation method of tantalum pentachloride, which has the purity of more than 99.999 percent, and compared with the existing product, the purity of the tantalum pentachloride prepared by the method is higher, so that the internal impurity elements in the tantalum pentachloride are prevented from being transferred to a terminal product, and the stability of the terminal product is effectively improved.
2. The invention provides a preparation method of tantalum pentachloride, which comprises the steps of firstly reacting high-purity chloridizing gas with tantalum powder, tantalum blocks or tantalum particles, purifying the tantalum pentachloride prepared after the reaction by multiple times of rectification of a specific process, wherein the purity of the prepared tantalum pentachloride is as high as 99.999 and above, the preparation method of the high-purity tantalum pentachloride is effectively enriched, and the product quality of a high-purity tantalum target material taking tantalum pentachloride as a precursor is improved.
3. The device can perform reaction and purification to obtain high-purity tantalum pentachloride. The device has reasonable structure and can improve the effect of twice the effort of purification.
Drawings
Fig. 1 is a schematic view of the overall structure of the device of the present invention.
In the drawing, a reaction kettle 1, a rectification conveying pipe 2, a reaction kettle feed inlet 3, a chlorinated gas steel cylinder 5, an inert gas steel cylinder 6, a tower kettle 8, a 9 armoured heater, a cooling jacket 10, a rectification tower 11, a tower top sampling port 13, a tower top discharge port 14 and a tower top 15 are arranged.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, other embodiments that may be obtained by other persons skilled in the art without making any inventive effort are within the scope of the present invention. Wherein the methods are conventional methods unless otherwise specified, and the starting materials are commercially available from the public sources unless otherwise specified.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The reaction equation involved in the invention is as follows:
2Ta (s) +5Cl 2(g) ＝2TaCl 5(s) ；2Ta (s) +10HCl (g) ＝2TaCl 5(s) +5H 2(g) 。
example 1
Referring to fig. 1, the invention provides a tantalum pentachloride preparation device, which comprises a reaction kettle 1 and a rectifying tower 11. The reaction kettle 1 is a reaction kettle with a heating function or a reaction kettle without a heating function and is connected with a heating device, and in any case, no matter the reaction kettle is externally provided with the heating device or is provided with the heating device, the reaction kettle 1 can realize the heating effect when the temperature needs to be raised, so that the kettle body is heated.
The reaction kettle 1 is also connected with a vacuum pump.
The reaction kettle 1 is provided with a reaction kettle feed inlet 3 for adding raw material tantalum. The material of the reaction kettle 1 is made of high-temperature-resistant and corrosion-resistant alloy materials, such as Monel alloy, nickel-based alloy or 316L stainless steel. The rectifying tower 11 is made of high-temperature-resistant and corrosion-resistant alloy materials, such as monel, nickel-based alloy or austenitic stainless steel.
The reaction kettle is connected with a chloridizing gas steel bottle 5 and an inert gas steel bottle 6, and a discharge port of the reaction kettle 1 is connected with a feed port of a rectifying tower 11; the rectifying tower 11 comprises a tower kettle 8 and a tower top 15, wherein the tower top 15 is positioned above the tower kettle and is communicated with the tower kettle, and a cooling device and a heater are arranged on the tower kettle 8.
The cooling device is a cooling jacket 10 arranged on the periphery of the tower kettle 8, and the heater is an armored heater 9 arranged at the bottom of the tower kettle 8.
The tower top 15 is provided with a tower top sampling port 13 and a tower top discharge port 14; the tower kettle 8 and the tower top 15 are connected through a rectification conveying pipe 2.
The device can be used for preparing tantalum pentachloride, and the device is organically combined with the preparation method, so that the high-purity tantalum pentachloride can be obtained with half effort.
Example 2
The invention provides a preparation method of tantalum pentachloride, which comprises the following steps,
s1, tantalum with the purity of 99% is filled into a reaction kettle 1, the filling amount is controlled to be 5% of the volume of the reaction kettle, then an inlet of the reaction kettle 1 is respectively connected with a chlorine gas steel bottle 5 with the purity of 99.0% and a nitrogen gas container 6 with the purity of 99.0%, nitrogen gas is introduced into the reaction kettle 1 after the pipeline connection is finished, the pressure is 0.01MPa, a vacuum pump is started to pump the system to-0.1 MPa after the preset pressure is reached, and the system is repeatedly replaced for 5 times;
in this embodiment, monel is selected as the material of the reaction kettle 1 and the material of the rectifying tower 11.
S2, heating the reaction kettle, heating at a speed of 30 ℃/h, starting to open a bottle valve of a chlorinated gas steel bottle 5 after the temperature of the reaction kettle 1 reaches 300 ℃, controlling the air inflow of chlorine gas to be 2.0kg/h in the embodiment of a chlorine gas steel bottle with the purity of 99.0%, and reacting chlorine gas with tantalum blocks in the reaction kettle 1 for 1.0h.
And S3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, wherein the number of tower plates of a rectifying section of the rectifying tower is 60. The rectifying tower comprises a tower kettle 8 and a tower top 15 which is arranged above the tower kettle 8 and communicated with the tower kettle, the temperature of the tower kettle 8 is firstly reduced, the temperature is controlled to be minus 90 ℃, and the temperature is kept for 0.5 hour. And after the reaction is finished, starting a heater to heat the tower kettle 8, wherein the heating temperature is 200 ℃, heating and sublimating the tantalum pentachloride solid phase into a gas phase, controlling the pressure of the rectifying kettle to be 0.01MPa, and keeping the pressure for 2.0 hours.
And S4, conveying the product obtained after the reaction in the step S2 to a rectifying tower, heating the tower top 15 of the rectifying tower to 100 ℃, and keeping the temperature for 0.5 hour, wherein the purpose is to promote the liquid phase reflux of tantalum pentachloride, and sampling and detecting after repeating the steps S3 and S4 for 2 times.
Sampling is carried out from a tower top sampling port 13 at the top of the rectifying tower, detection is carried out by using an infrared gas analyzer and gas chromatography, the detection results are shown in table 1, and after the tantalum pentachloride index is qualified, product filling is carried out through a tower top discharge port 14 of the rectifying tower.
TABLE 1
Example 3
The invention provides a preparation method of tantalum pentachloride, which comprises the following steps,
s1, loading tantalum with purity of 99.9% into a reaction kettle 1, controlling the loading amount to be 20% of the volume of the reaction kettle, respectively connecting an inlet of the reaction kettle 1 with a chlorine gas steel bottle 5 with purity of 99.99% and an argon gas container 6 with purity of 99.9%, introducing argon gas into the reaction kettle 1 after the pipeline connection is finished, controlling the pressure to be 0.10MPa, starting a vacuum pump to pump the system to-0.1 MPa after the preset pressure is reached, and repeatedly replacing for 10 times;
in this embodiment, the material of the reaction kettle 1 and the material of the rectifying tower 11 are both nickel-based alloys.
S2, heating the reaction kettle, heating according to the speed of 80 ℃/h, starting to open a bottle valve of a chloridized gas steel bottle 5 after the temperature of the reaction kettle 1 reaches 500 ℃, controlling the air inflow of hydrogen chloride to be 5.0kg/h in the embodiment of a chloridized gas steel bottle with the purity of 99.9%, and reacting hydrogen chloride with tantalum blocks in the reaction kettle 1 for 3.0h.
And S3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, wherein the number of tower plates of a rectifying section of the rectifying tower is 80. The rectifying tower comprises a tower kettle 8 and a tower top 15 which is arranged above the tower kettle 8 and communicated with the tower kettle, the temperature of the tower kettle 8 is firstly reduced, the temperature is controlled to be minus 60 ℃, the temperature is kept for 1 hour, a heater is started to heat the tower kettle 8 after the reaction is finished, the heating temperature is 400 ℃, the tantalum pentachloride is heated and sublimated into a gas phase through solid phase heating, the pressure of the rectifying kettle is controlled to be 0.10MPa, and the holding time is 1.0 hour.
And S4, conveying the product obtained after the reaction in the step S2 to a rectifying tower, heating the top 15 of the rectifying tower to 110 ℃, and keeping the temperature for 1.0 hour, wherein the purpose is to promote the liquid phase reflux of tantalum pentachloride, and sampling and detecting after repeating the steps S3 and S4 for 5 times.
The sample is taken from the top sampling port 13 at the top of the rectifying tower, and is detected by an infrared gas analyzer and gas chromatography, the detection result is shown in table 2, and after the tantalum pentachloride index is qualified, the product filling is started through the top discharge port 14 of the rectifying tower.
TABLE 2
Example 4
The invention provides a preparation method of tantalum pentachloride, which comprises the following steps,
s1, loading tantalum with the purity of 99.99% into a reaction kettle 1, controlling the loading amount to be 40% of the volume of the reaction kettle, connecting an inlet of the reaction kettle 1 with a chlorine gas steel bottle 5 and a helium gas container 6 with the purity of 99.999% respectively, introducing helium gas into the reaction kettle 1 after the connection of a pipeline is finished, controlling the pressure to be 0.15MPa, and starting a vacuum pump to pump the system to-0.1 MPa after the preset pressure is reached, and repeatedly replacing for 20 times;
in this embodiment, monel is selected as the material of the reaction kettle 1 and the material of the rectifying tower 11.
S2, heating the reaction kettle, heating according to the speed of 120 ℃/h, starting to open a bottle valve of a chloridized gas steel bottle 5 after the temperature of the reaction kettle 1 reaches 850 ℃, controlling the air inflow of hydrogen chloride to be 8.0kg/h in the embodiment of a chloridized gas steel bottle with the purity of 99.9999%, and reacting hydrogen chloride with tantalum blocks in the reaction kettle 1 for 5.0h.
And S3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, wherein the number of tower plates of a rectifying section of the rectifying tower is 90. The rectifying tower comprises a tower kettle 8 and a tower top 15 which is arranged above the tower kettle 8 and communicated with the tower kettle, the temperature of the tower kettle 8 is firstly reduced, the temperature is controlled to be 0 ℃, the temperature is kept for 3 hours, a heater is started to heat the tower kettle 8 after the reaction is finished, the heating temperature is 650 ℃, the tantalum pentachloride is heated and sublimated into a gas phase through solid phase heating, the pressure of the rectifying kettle is controlled to be 0.30MPa, and the holding time is 0.5 hour.
And S4, conveying the product obtained after the reaction in the step S2 to a rectifying tower, heating the tower top 15 of the rectifying tower to 200 ℃, and keeping the temperature for 0.5 hour, wherein the purpose is to promote the liquid phase reflux of tantalum pentachloride, and sampling and detecting after repeating the steps S3 and S4 for 10 times.
Sampling is carried out from a tower top sampling port 13 at the top of the rectifying tower, detection is carried out by using an infrared gas analyzer and gas chromatography, the detection results are shown in table 3, and after the tantalum pentachloride index is qualified, product filling is carried out through a tower top discharge port 14 of the rectifying tower.
TABLE 3 Table 3
Example 5
The invention provides a preparation method of tantalum pentachloride, which comprises the following steps,
s1, loading tantalum with the purity of 99.99% into a reaction kettle 1, controlling the loading amount to be 40% of the volume of the reaction kettle, connecting an inlet of the reaction kettle 1 with a chlorine gas steel bottle 5 and a helium gas container 6 with the purity of 99.999% respectively, introducing helium gas into the reaction kettle 1 after the connection of a pipeline is finished, controlling the pressure to be 0.15MPa, and starting a vacuum pump to pump the system to-0.1 MPa after the preset pressure is reached, and repeatedly replacing for 20 times;
in this embodiment, monel is selected as the material of the reaction kettle 1 and the material of the rectifying tower 11.
S2, heating the reaction kettle, heating according to a speed of 70 ℃/h, starting to open a bottle valve of a chloridized gas steel bottle 5 after the temperature of the reaction kettle 1 reaches 350 ℃, controlling the air inflow of hydrogen chloride to be 8.0kg/h in the embodiment of a chloridized gas steel bottle with the purity of 99.9999%, and reacting hydrogen chloride with tantalum blocks in the reaction kettle 1 for 5.0h.
And S3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, wherein the number of tower plates of a rectifying section of the rectifying tower is 90. The rectifying tower comprises a tower kettle 8 and a tower top 15 which is arranged above the tower kettle 8 and communicated with the tower kettle, the temperature of the tower kettle 8 is firstly reduced, the temperature is controlled to be 0 ℃, the temperature is kept for 2 hours, a heater is started to heat the tower kettle 8 after the reaction is finished, the heating temperature is 650 ℃, the tantalum pentachloride is heated and sublimated into a gas phase through solid phase heating, the pressure of the rectifying kettle is controlled to be 0.30MPa, and the holding time is 0.5 hour.
And S4, conveying the product obtained after the reaction in the step S2 to a rectifying tower, heating the tower top 15 of the rectifying tower to 190 ℃, and keeping the temperature for 3 hours, wherein the purpose is to promote the liquid phase reflux of tantalum pentachloride, and sampling and detecting after repeating the steps S3 and S4 for 6 times.
The tantalum pentachloride in examples 2-4 was sampled and tested as follows:
(1) And (3) detecting by an infrared gas analyzer: the infrared gas analyzer is adopted to detect the prepared product, and the detection is carried out according to the standard of the GB/T25903-2010 infrared gas analyzer test method.
(2) And (3) gas chromatography detection: detection is carried out according to the standard of GB/T37182-2018 gas analysis plasma emission gas chromatography.
As shown in tables 1, 2 and 3, the results of the tests were substantially identical, and the purity of tantalum pentachloride in examples 1 to 3 was obtained from the results of the tests in tables 1, 2 and 3, and the results of the tests were indicative that the purity of tantalum pentachloride prepared by the apparatus and method for preparing tantalum pentachloride of the present invention was 99.9% or more.
In summary, the detection result shows that the tantalum pentachloride prepared by the device and the method for preparing tantalum pentachloride meets the requirements, and the consistency of the quality of the terminal product is ensured.
Comparative example
S1, tantalum with the purity of 99% is filled into a reaction kettle 1, the filling amount is controlled to be 5% of the volume of the reaction kettle, then an inlet of the reaction kettle 1 is respectively connected with a chlorine gas steel bottle 5 with the purity of 99.0% and a nitrogen gas container 6 with the purity of 99.0%, nitrogen gas is introduced into the reaction kettle 1 after the pipeline connection is finished, the pressure is 0.01MPa, a vacuum pump is started to pump the system to-0.1 MPa after the preset pressure is reached, and the system is repeatedly replaced for 5 times;
in this embodiment, monel is selected as the material of the reaction kettle 1 and the material of the rectifying tower 11.
S2, heating the reaction kettle, heating at a speed of 30 ℃/h, starting to open a bottle valve of a chlorinated gas steel bottle 5 after the temperature of the reaction kettle 1 reaches 200 ℃, controlling the air inflow of chlorine gas to be 2.0kg/h in the embodiment of a chlorine gas steel bottle with the purity of 99.0%, and reacting chlorine gas with tantalum blocks in the reaction kettle 1 for 1.0h.
And S3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, wherein the number of tower plates of a rectifying section of the rectifying tower is 50. The rectifying tower comprises a tower kettle 8 and a tower top 15 which is arranged above the tower kettle 8 and communicated with the tower kettle, the temperature of the tower kettle 8 is firstly reduced, the temperature is controlled to be 5 ℃, and the temperature is kept for 0.5 hour. And after the reaction is finished, starting a heater to heat the tower kettle 8, heating at 700 ℃, heating and sublimating the tantalum pentachloride solid phase into a gas phase, controlling the pressure of the rectifying kettle to be 0.01MPa, and keeping the pressure for 2.0 hours.
And S4, conveying the product obtained after the reaction in the step S2 to a rectifying tower, heating the tower top 15 of the rectifying tower to 250 ℃, and keeping the temperature for 0.5 hour, wherein the purpose is to promote the liquid phase reflux of tantalum pentachloride, and sampling and detecting after repeating the steps S3 and S4 for 2 times.
Sampling is carried out from a tower top sampling port 13 at the top of the rectifying tower, detection is carried out by using an infrared gas analyzer and gas chromatography, the detection results are shown in table 1, and after the tantalum pentachloride index is qualified, product filling is carried out through a tower top discharge port 14 of the rectifying tower.
The difference between this comparative example and example 2 is that there is a difference in the control of the temperature of the reaction vessel in step S2, a difference in the number of trays of the rectifying column in step S3, a difference in the heating temperature of the column bottom 8, and a difference in the heating temperature of the column top 11 in step S4. The sample is taken from the top sampling port 13 at the top of the rectifying tower, and is detected by an infrared gas analyzer and gas chromatography, the detection results are shown in table 4, and after the tantalum pentachloride index is qualified, the product filling is started through the top discharge port 14 of the rectifying tower.
At present, the technical scheme of the invention has been subjected to pilot-scale experiments, namely small-scale experiments of products before large-scale mass production; after the pilot test is completed, the use investigation of the user is performed in a small range, and the investigation result shows that the user satisfaction is higher; now, the preparation of the formal production of the product for industrialization (including intellectual property risk early warning investigation) is started.
The above-described embodiments are preferred examples of the invention and are not exhaustive of the possible implementations of the invention. Various modifications of the invention, which are apparent to those skilled in the art, should be deemed to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of tantalum pentachloride is characterized by comprising the following steps of,
s1, loading tantalum with purity of more than 99% into a reaction kettle, controlling the loading amount to be 5% -40% of the volume of the reaction kettle, replacing gas in the reaction kettle with inert gas or nitrogen, vacuumizing, and repeating the operation for 5-20 times;
s2, heating the reaction kettle at the temperature of 300-850 ℃, introducing chlorine or hydrogen chloride into the reaction kettle, and reacting for 1.0-5.0 hours;
s3, conveying the product obtained after the reaction in the step S2 to a rectifying tower, wherein the rectifying tower comprises a tower kettle and a tower top which is arranged above the tower kettle and is communicated with the tower kettle, firstly cooling the tower kettle, controlling the temperature to be between-90 and 0 ℃, keeping the temperature for 0.5 to 3.0 hours, then heating the tower kettle at 200 to 650 ℃, controlling the pressure of the rectifying tower to be between 0.01 and 0.30MPa, and keeping the temperature for 0.5 to 2.0 hours;
s4, heating the tower top at 100-200 ℃, maintaining the temperature for 0.5-4.0 hours, repeatedly sampling and detecting for 2-10 times, and discharging after the tantalum pentachloride index is qualified.
2. The method for preparing tantalum pentachloride according to claim 1, wherein in step S1, the inert gas is argon or helium, and the purity is 99.0% -99.999%.
3. The method for preparing tantalum pentachloride according to claim 1, wherein in step S1, inert gas is filled in the reaction kettle to a pressure of 0.01-0.15 MPa, and then the reaction kettle is vacuumized to-0.1 MPa.
4. The method for preparing tantalum pentachloride according to claim 1, wherein in the step S2, the purity of the introduced chlorine gas or hydrogen chloride is 99.0% -99.9999%, the heating temperature of the reaction kettle is 350-800 ℃, the heating rate is 30-120 ℃/h, and the air inflow amount of the chlorine gas or hydrogen chloride is 2.0-8.0 kg/h.
5. The method for producing tantalum pentachloride according to claim 1, wherein in step S4, a top heating temperature is 110 to 190 ℃.
6. The tantalum pentachloride preparation device is characterized by comprising a reaction kettle (1) and a rectifying tower (11), wherein the reaction kettle is connected with a chlorinated gas steel cylinder (5) and an inert gas steel cylinder (6), and a discharge port of the reaction kettle (1) is connected with a feed port of the rectifying tower (11); the rectifying tower (11) comprises a tower kettle (8) and a tower top (15) which is arranged above the tower kettle and communicated with the tower kettle, and a cooling device and a heater are arranged on the tower kettle (8).
7. The tantalum pentachloride preparation device according to claim 6, wherein the reaction kettle (1) is a reaction kettle with a heating function or is connected with a heating device.
8. The tantalum pentachloride preparation device according to claim 6, wherein the cooling device is a cooling jacket (10) arranged on the periphery of the tower kettle (8), and the heater is an armored heater (9) arranged at the bottom of the tower kettle (8).
9. The tantalum pentachloride preparation device according to claim 6, wherein a reaction kettle feed port (3) is arranged on the reaction kettle (1); the tower top (15) is provided with a tower top sampling port (13) and a tower top discharge port (14);
the tower kettle (8) is connected with the tower top (15) through a rectification conveying pipe (2).
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